Abstract An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et 4N +) and tetrafluoroborate (BF 4 −) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et 4N + into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li +. For the positive electrode, BF 4 − was shown to intercalate above +4.3 V versus Li/Li +. The characteristic G-band doublet peak ( E 2g2( i) (1578 cm −1) and E 2g2( b) (1600 cm −1)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm −1) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm −1) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).